Azo compounds



Patented Feb. 27, 1940 UNITED STATES PATENT OFFICE AZO COMPOUNDS Arthur R. Murphy, deceased, late of Penns Grove, N. J.,.by Margaret R. Murph administratrix, Penns Grove, N. J., and Swanie S. Rossander, Wilmington, Del., assignors to E. I. du Pont de Nemours & Company, Wilmington, Del.,'a corporation of Delaware No Drawing. Application August 26, 1937,

Serial No. 161,037

7 Claims.

This invention relates to azo compounds which cotton, regenerated cellulose and related materials which can be diazotized on the fiber and coupled with azo dye. coupling components to give dyeings of superior fastness to washing. Another object is to provide dyestuffs'which have good discharge properties after they are developed on the fiber. Another object is to provideproc- Other objects of the invention will be apparent from the following esses for making the dyestuffs.

description: I

The'objects of the invention are attained in general by producing azo compounds of the general type in which -R1-XR2--, has two aryl groups, R1 and R2 which are joined directly or by an intervening group -X.which may consist of any of the groups I pling component.

hours and warmed to C. Salt (10% by and R1 and at are substituted or unsubstituted benzene or naphthalene nuclei; Y represents alkyl or carboxyl; and. R3 is the aryl nucleus of an azo dye coupling component substituted by a diazotizable amino group.

The invention will be more fully understood by'reference to the following description and to the examples which illustrate but do not limit the invention.

' Example 1 5.5 parts of para amino benzoyl meta phenylene diamine which were slurried with 300 parts of water were dissolved by adding 12 parts of 10 normal hydrochloric acid and cooled to 5 C. 25 parts of 2 normal sodium nitrite were added as rapidly as the nitrite was absorbed, and an excess of nitrite was maintained for 20 minutes while cooling to 0-5 C.

Y 'A solution of 12.2 parts of l-meta-aminophenyl-5-pyrazolone-3-carboxylic acid in 500 parts of water was made, and the solution was made slightly alkaline to brilliant yellow paper by adding soda 'ash. Then parts of 2 normal soda ash solution were added and the solution was cooled to 5 C. v v

The tetrazo of para-amino-benzoyl-meta-phenylene-diamine was slowly added to the solution of 1-meta-amino-phenyl-5-pyrazolone-3-carboxylic acid while maintaining strong alkalinity to brilliant yellow paper and an excess of the cou- The mixture was stirred 3 weight of the solution) was added. The mixture was stirred hour and filtered.

The coupling product was slurried with 800 parts of water for 4 hours andv 25 parts of 2 normal sodium nitrite were added. The mixture was stirred rapidly while adding 18 parts of 10 normal hydrochloric acid and an excess of nitrite was maintained for 2 hours while keeping the temperature at 20-23 C. The excess nitrite was removed by adding a small amount of urea.

A solution of 11.9 parts mixed Cleves acid in. 500 parts of water was made by slowly adding soda ash (approximately. 2.8 parts) until the Cleves acid was dissolved .to a clear solution which was slightly acid to litmus; The solution of Cleves acid was added to the above tetrazo mediately added. This solution was neutral to Congo red paper and was stirred 4 hours at 20-25 G. Then soda ash was slowly added to the mixture during one hour until it was slightly alkaline to brilliant yellow paper and it was stirred one hour. The mixture was slowly warmed to 80 C. and made distinctly alkaline to brilliant yellow paper by adding more soda ash. Salt (twenty per cent by volume) was added to a fairly clear rim and the precipitate was filtered. The product was then dried at 90-100 C. The product was brown in appearance. The probabl formula of the dye is: y I

ylic acid was maintained. The mixture was stirred 3 hours, slowly warmed to 75 C. and salt was added (10% by weight of the solution). The mixture was stirred hour and filtered.

The residue was stirred with 800 parts of water for four hours to a fine slurry and 23 parts of 10" normal hydrochloric acid were added. Then'30 parts of 2 normal sodiumnitrite were added and the mixture was stirred 3 hours at 20-25 C. with a strong excess of nitrite.

19.8parts of para-a1nino-benzoyl-J-acid in 7 parts of water were stirred to a smooth slurry and ammonia (approximately 4% cc. of 27%) was added to. complete solution which wasslight- IIT=N(iJ-(IJ-CO2Na H 0 N N\ o=o l SOINB, N

HzN N=N This compound was soluble in water and was capable of being diazotized by methods well known in the art.

It was substantive to fibers of cotton and regenerated cellulose and when fabrics of these materials were dyed with the compound and diazotized on the fibre a dye having superior fastness to washing was produced by development with azo dye coupling components such as beta naphthol, l-phenyl3-methyl-5pyrazolone, resorcinol, meta-tolylene-diamine and the like. These dyes were discharged with a discharging agent and pure whites were produced.

' Example 2 9.7 parts of benzidine 3:3'-disulfonic acid were dissolved in 300 parts of water at 20 C; with the minimum amount of soda ash necessary and cooled to 5 C. 18 parts of 10 normal hydrochloric acid wereadded and then 25 parts of 2' normal sodium nitrite were added as rapidly as the nitrite was absorbed. Acidity to Congo red paper and a slight excess of nitrite were .maintained for hour at a temperature of 5 C.

12 parts of 1-meta-amino-phenyl-5-pyrazolone 3-carboxylic acid were slurried in 500 parts water at 20 C. and soda ash was added until the solution was slightly alkaline to brilliant yellow paper.

Then parts 2 normal soda ash solution were.

added and the solution was cooled to 10 C.

The tetrazo of benzidine 3:3disulfonic acid was added to the alkaline solution of l-metaamino-phenyl-5-pyrazolone 3 carboxylic acid during 15 minutes, while the mixture was kept alkaline to brilliant yellow paper and an excess of 1-meta-amin0-phenyl-5-pyrazolone-3-carbox the heading Direct.

1y alkaline to brilliant yellow paper. 200 parts of 2 normal soda ash solution were added'andlthe mixture was cooled to 16 C. The'previously prepared tetrazo solution was slowly added to the para-amino-benzoyl-J-acid. solution while maintaining strong alkalinity to brilliant yellow paper and an excess of para-amino-benzoyl-J-acid in the mixture. The mixture was stirred 4 hours,

. slowly warmed to 75 (2., salted and filtered. The

product was dried at 90-95 C. It was a reddish dry powder." Its probable formula is Except forsma ll differences in shade this product had the desirable properties of the product of Example 1.

The following compounds were made by procedures similar to the procedures of the above excoupled to' two moles of the aminesunder the heading 3rd component. -The fiber was dyed with the tetrakisazo ccmpound resulting'from the last coupling giving colors of direct dyeings under The direct dyeing was then subjected to tetrazotization and the final dye was developed with beta-naphthol, giving colors under the heading Developed. The dyes, in

The

NHCOONH;

general, are characterized by their fas'tness to washing and their excellent discharge properties;

The pyrazolone group is a 1'- (amino-phenyl) -pyrazolone compound which in the benzene nu- 5 I v v Shades of dyeing 2nd component 3rdcoinpo'nent 1st component (2 moles) (21mm) Developed Dire (b-naphthol) 3 3:3'-diamino azoxybenzone-.- 1 (m amino -'pl1onyl). 5 i-naphthylamine-B-sulfonicacid- Yelloworange. Brown.

pyrazolone 3 carboxylic B01 4 p Amino benzoyl In .....do i-naphthylamine-(mixed 6 and n Do.

phenylene diamine. 7)-snlionic acid. 5 .....do.... 2 mnino-6-naphthol-7esul- Orange Reddish brown.

' 011680 6 ..do. .,2(p-amino benzoyl) naphthyla- .do Orange.

mine 5 napththol 7 sul- Ionic acid. 7 -do do l-(m-aminophenyD-B-pyraz- Yellow Do.

' olone-t-carboxylic acid. 8 Benzidine 3:3'-disnlionic acid" 1 meta amino phony] 3 1 metaamino phenyl -3 do Do.

, methyl-S-pyrazolone. I methylJz-pyrazolone. 9 d0. 1 meta jamino'- phenyl 5 do D0.

pyrazolono'Zi-carbo xylic acid. 10 do Cresidine Orange Red. 11 --..-d0 I-acid Red-orange.-. Do. 12 .don (Para-amino-benzoyl)J-acid. Orange Orange. 13 -....do 1 meta -.aminophenyl 5 Oresidine' do Brown.

pyrazolone-B-carboxylic acid.

. v v a Examples 7, 8, and 9 give yellow dyes when developed with l-phenyl-3-methyl-firpyrazolone. These dyeings have superior fasmess to washing. g

The dyestuffs are represented generally by the cleus may be unsubstituted or substituted by alformula kyl, alkoxy, halogen sulfonic acid or carboxyl. H The amino group is preferably in the 3-position of the aryl nucleus and the pyrazolone ring may be I I! X additionally substituted by methyl or carboxyl in 5% the 3-position thereof p 7 The end component of the dyestuii is any azo H dye coupling component having a diazotizab-le I amino group, such as amino benzenes, naphthyl- T x amines, hydroxy substituted amino-benzenes and C I =N naphthylamines and amino-substituted phenyl- N pyrazolones. The aryl nuclei of these compounds I i may be unsubstituted or they may be substituted The group -R1Z"R2 is the residue after Once or more than once y alkyl, xy al n, diazotization of a di-amino-aryl compound havhydroxy, sulfonlc acid and carboxyl. In coupling jng t aryl i, R1 and R2 'lik r lik some unsubstituted compounds such as aniline benzene or naphthalene nuclei which may be unit is necessary to u e Omega Sulfonic acid substituted or substituted once or more than oncev ""IlVatlVe as the pa Substance and e y by alkyl, alkoxy, sulfonic acid, carboxyl or haloly e a t up e t r d t dlazotlzabl'e gen, such as chloro, bromo, methyl, ethyl, propyl, o l p- OtherWlSe e parent su e butyl, the corresponding alkoxygroups and still descrlbedean er l ybe d y Q ll others. The amino groups must be present in economlcally p odu m dy stufis havme generdifferent aryl nuclei and be capable of diazotizaally good prepert est e" o of benzene tion, either concurrently or consecutively in ord pht l e-p b Others can der to produce a tetrazo compound; The two be used withgoodresults. Y aryl nuclei may be directly united, such as di- .Amongthe preferred mpounds be 0011- amino derivatives of diphenyl or they may be pled as the end components are'l-naphthylarnineunited by intermedia'te.glellps-v e IfOIIOWiIIg G-sulfonic acid;l-naphthylamine-7-sulfonic acid are illustrations of compounds which can be used and m t t e c nd instead of diphenyl compounds and the intermee o u containing 2 t 4 solubilizing (hate groups e W groups; such as sulfonic acid and carboxyl have 4:4'-di-amino-stilbene OH= ,H' the'r'n'ost desired solubility. Products containing 4:4'-di amino-di-benzyl -CHzCH:' two sulfonic acid groups and two carboxyl groups 4z4'-di-amino-diphenyl methane CH,- are preferred. The .carboxyl groups are prefer- 4:4-di-amino-diphenyl ether '0 ably substituted in the pyrazolone ring and the sulfonic acid groups'are present in the end com- 4:4-dia.mino-benzophenone G "ponents. a:s'-di-amino-azoxy-bnze e azoxy" h In the preferred embodiments the aryl nuclei of I the middle di-aryl-diamine are substituted or bstituted benzene nuclei with an intervening h 1 a N0- unsumAmino benzoylmp any one lamina O H H 0 azoxy or NHCO gr up, the py e g ll 1 I II is substitutedby carboxyand the end groups are 1=3-di(amim'benmyl'amim)'bmene naphthylamines substituted by sulfonic acid in 1 4 the 6 or '7 positions with respect to the amino 4-amlno-naphthoyl-m-phenylene diamine O N-- groups. 7

nuclei which are substituted once by one of 'a Since from the foregoing description" of the inboxy and sulfonic acid; Z isone of a group 0011+; vention it will be apparent to those skilled in the SiSting art that many embodiments of the invention may be made without departing from the spirit and i 5 scope thereof, it is to be understood that no limi- H o o H H O 0 H tations are intended in the annexed claims except 1 [I [I 1 by the prior art. and n is an integer not greater than 2, said compound having at least two solubilizing groups.

1. A dye which in the form of its acid is repin which Arylz is the radical resented by the formula I ll R R 0:0 in which Z is one of the group consisting of N N 30 --CH=CH, -CHaCHr-, CH2, o, azoxy, N=N-11; R, N=N- f i i if I l C,CNCaH;-N Cand-O in which each R2 is the residue after coupling of d t t I t th 2 one of a group consisting of a l-(amino phenyl) an IS an m eger no grea' er an 5-pyrazo1one carboxylic acid, a l-(amino phenyl) 3. A compound represented by the formula H H a I v 40 o P 1ii:N=N-iir 1,-1 I=Ne --%-oHi v n N\ o=o 0=o /N i fOzNar I? "N some HaN in which Z is one of the group consisting of 3-methy1-5-pyrazolone, compounds having benzene, naphthalene, hydroxy benzene and naphthol group consisting of amino and amino-benzoylamino and derivatives of said'amino benzenes, naphthylamines, hydroxy benzenes and naphthols in which the aryl nuclei are substituted by not K i r i more than two members of a group consisting of 2-* 37,,

alkyl, alkoxy and sulfonic acid; each Y is one of a group consisting of methyl and carboxy; each 1 ll arylz is one of a group consisting of benzene and 5 naphthalene radicals; R is from the group cone and n is an integer not greater than 2. x sisting of hydrogen, alkyl, alkoxy, halogen, care 4. A compound represented by the formula i NaO:C-C-C-N -N H 5 /C::0 Qo-O-N-No-o-oo Na SO Na N Y l H n g I o=c\ I III some HzN N=N- I NH:

7. The process which comprises coupling two molecular proportions of a 1-(amino-phenyD-5- pyrazolone carboxylic acid to one molecular proin which SOaNa is in one of the positions-6 and 7 with respect to the amino group.

5. A compound represented by the formula.

SOzNa N portion of a fully diazotized compound of the type in which -SO3Na is in one of the positions 6 and '7 with respect to the amino group.

6. The process which comprises coupling two molecular proportions of a 1-(amino-phenyD-5- o pyrazolone to one molecular proportion of a. fully diazotized di-amino-aryl compound represente by the formula inwhich Z is one of the group consisting of in which Arylz is one of the group consisting of benzene and naphthalene nuclei, M is one of the group consisting of hydrogen, alkyl, alkoxy, halogen, carboxyl and sulfonic acid, Z is one of 25 the group consisting of and n is an integer not greater than 2, diazotizing the product of coupling and. coupling to an azo. dye coupling component which is substituted by a diazotizable amino group.

I MARGARET R. MURPHY, Administratrizc of the Estate of Arthur R.

Murphy, Deceased.

SWANIE S. ROSSANDER.

m CH=CH, CHr-CHr-, CH:----, -0, -(J-, azoxy,

i if i i if I I? 'N-o, CNCuH4-N-C- and oN,

and n is an integer not greater than 2, diazotizing the product of coupling and coupling totwo molecular proportions of a primary amino-arylsulfonic acid.

'Patent No. 2,191, 00.

- CERTIFICATE OF CORRECTION.

I February 27, 19LLO.

MARGARETLR. MURPHY, ADMI NISTRATRIX 'of ARTHUR R. MURPHY; ET AL. It is hereby cei'tlfied that errorappears in the printe dspecification of the above rix'nnbered patent requiring correction as follows: Page 5, first colunin, line 59-1 0, for that portion of the formula appearing as }/I read and'that the saidLettei's Patent should be rea l with this 00 I rection therein that the same may cdnfofm to the re oordiof the case in the Patent Office.

Signed and sealedthis Zhd day of April; A51). 19m.

Henry Van Arsdale,

(Seal). Acting Comissioner of Patents. 

